Designation: C560 88 (Reapproved 2010)1

An American National Standard

Standard Test Methods for

Chemical Analysis of Graphite1

This standard is issued under the xed designation C560; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon () indicates an editorial change since the last revision or reapproval.

1 NOTEUpdated 57.1 editorially in May 2010.

1. Scope 1.1 These test methods cover the chemical analysis of graphite. 1.2 The analytical procedures appear in the following order:
Silicon by the Molybdenum Blue (Colorimetric) Test Method Iron by the o-Phenanthroline (Colorimetric) Test Method Calcium by the Permanganate (Colorimetric) Test Method Aluminum by the 2-Quinizarin Sulfonic Acid Test Method Titanium by the Peroxide (Colorimetric) Test Method Vanadium by the 3,38-Dimethylnaphthidine (Colorimetric) Test Method Boron by the Curcumin-Oxalic Acid (Colorimetric) Test Method Sections 8 to 14 15 to 21 22 to 28 29 to 35 36 to 43 44 to 51 52 to 59

TABLE 1 Concentration of Elements, Limits of Sensitivity, and Reproducibility

Concentration Range, g/mL Solution 10 to 100 g/100 mL 100 to 600 g/100 mL 600 to 3000 g/100 mL 10 to 100 g/100 mL 600 to 3000 g/100 mL 10 to 130 g/50 mL 0.5 to 1.4 g/50 mL Reproducibility, Relative, % (s/x 3 100) 64 65 65 60.1 62 65 620

Element Silicon Iron Calcium Aluminum Titanium Vanadium Boron

Sensitivity Limit, g/mL Solution 1 g/100 mL 40 g/100 mL 50 g/100 mL 2 g/100 mL 200 g/100 mL 5 g/50 mL 0.1 g/50 mL

1.3 The preferred concentration of sought element in the nal solution, the limits of sensitivity, and the precision of the results are given in Table 1. 1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. See 56.1 for specic caution statement. 2. Referenced Documents 2.1 ASTM Standards:2 C561 Test Method for Ash in a Graphite Sample D1193 Specication for Reagent Water E29 Practice for Using Signicant Digits in Test Data to Determine Conformance with Specications
1 These test methods are under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and are the direct responsibility of Subcommittee D02.F0 on Petroleum Products and Lubricants Current edition approved May 1, 2010. Published May 2010. Originally approved in 1965. Last previous edition approved in 2005 as C560 88 (2005) e1. DOI: 10.1520/C0560-88R10E01. 2 For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards volume information, refer to the standards Document Summary page on the ASTM website.

3. Signicance and Use 3.1 These test methods provide a practical way to measure the concentration of certain trace elements in graphite. Many end uses of graphite require that it be free of elements which may be incompatible with certain nuclear applications. Other elemental contamination can affect the rate of oxidative degradation. 3.2 These test methods allow measurement of trace amounts of contaminants with a minimal amount of costly equipment. The colorimetric procedures used are accessible to most laboratories. 4. Reagents 4.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specications of the Committee on Analytical Reagents of the American Chemical Society, where such specications are available.3 Other grades may be used, provided it is rst ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination.
3 Reagent Chemicals, American Chemical Society Specications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.

Copyright. (c) ASTM International, 100 Barr Harbor Drive P.O. Box C-700 West Conshohocken Pennsylvania United States

Copyright by ASTM Int'l (all rights reserved);

C560 88 (2010)1
4.2 When available, National Institute of Standards and Technology (NIST) certied reagents should be used as standards in preparing calibration curves. 4.3 Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to Specication D1193. 4.4 National Institute of Standards and Technology certied reagents specied in certain steps of this procedure may no longer be available. If NIST reagents are not available, then the highest purity reagent grade shall be substituted. 5. Sampling 5.1 The entire sample of graphite should be crushed and ground to pass a No. 60 (250-m) sieve in a roll crusher. The sample may have been reduced in size initially by drilling the test bar with silicon carbide-tipped drills. 6. Rounding Calculated Values 6.1 Calculated values shall be rounded to the desired number of places in accordance with Practice E29. 7. Precision and Bias 7.1 No statement is being made about either the precision or bias of these test methods. At this time Committee C05 is investigating new standard methods of chemical analysis of graphite that will eventually replace these test methods. For this reason, no statistical study of these test methods has been planned. 7.2 The relative reproducibility data in Table 1 has no supportive research report on le and does not conform to ASTM precision and bias standards. SILICON BY THE MOLYBDENUM BLUE TEST METHOD 8. Summary of Test Method 8.1 Silicomolybdic acid is formed by adding ammonium molybdate to soluble silicates in acid solution. The heteropoly acid is reduced with stannous chloride to form a deep blue colloidal solution. Photometric measurement is made at 765 nm. Regular classical gravimetric methods for silica using sodium carbonate fusion followed by hydrouoric acid volatilization may be suitable for use. 9. Stability of Color 9.1 The blue colored solution should be disposed of and the determination repeated if a period of 12 h has elapsed between color development and measurements. 10. Interferences 10.1 There is no interference from the ions usually present in graphite. 11. Reagents 11.1 Ammonium Molybdate (50 g/L)Dissolve 50 g of ammonium molybdate ((NH4) 6-Mo7O244H2O) in water and dilute to 1 L. 11.2 Hydrochloric Acid (HCl) (1+1)Mix equal volumes of concentrated HCl, sp gr 1.19 and water.
Copyright by ASTM Int'l (all rights reserved);

11.3 Silicon, Standard Solution (1 mL = 1 mg Si)Dissolve 10.1 g of sodium silicate (Na 2SiO39H2O) in water and dilute to 1 L in a volumetric ask. Store in a polyethylene bottle. Determine exact concentration by the standard gravimetric procedure. 11.4 Silicon, Working Solution (1 mL = 0.01 mg Si)Dilute 10 mL of standard silicon solution (1 mL = mg Si) to 1 L in a volumetric ask. Transfer to a polyethylene bottle. 11.5 Sodium Carbonate Solution (100 g/L)Dissolve 100 g of sodium carbonate (Na2CO3) in water and dilute to 1 L. Store in a polyethylene bottle. 11.6 Stannous Chloride SolutionDissolve 2.5 g of stannous chloride (SnCl22H2O) in 5 mL of hot concentrated HCl (sp gr 1.19) and dilute to 250 mL with water. Prepare a fresh solution every 2 weeks. 11.7 Sulfuric Acid (H2SO4) (1+3)Carefully mix 1 volume of concentrated H2SO4, sp gr 1.84 with 3 volumes of water. 12. Preparation of Calibration Curve 12.1 Calibration SolutionsTransfer 0, 1.0, 3.0, 5.0, 7.0, and 10 mL of silicon working solution (1 mL = 0.01 mg Si) to 100-mL volumetric asks. Add 5 drops of H2SO4 (1+3) and dilute to approximately 10 mL. 12.2 Color DevelopmentAdd 2.5 mL of (NH4)6Mo7O24 solution to each ask and let stand 5 min. Then add 5.0 mL of H2SO4 (1+3), mix well, and add 5 drops of SnCl2 solution. Dilute to volume and let stand 5 min. 12.3 PhotometryTransfer a suitable portion of the reagent blank solution to a 1-cm absorption cell and adjust the photometer to the initial setting, using a wavelength of 765 nm. While maintaining this photometer adjustment, take the photometric readings of the calibration solutions. 12.4 Calibration CurvePlot the photometric readings (absorbance) of the calibration solution against micrograms of silicon per 100 mL of solution. 13. Procedure for Carbonate Fusion 13.1 Sample SolutionRinse the ash (from a 50 to 75-g ash sample) from the platinum dish into a mullite mortar with three 0.5-g portions of Na2CO3 passing a No. 100 (150-m) sieve (see Test Method C561). Grind the resulting mixture to pass a No. 200 (75-m) sieve to ensure intimate contact of the ash with the ux. Then transfer the mixture to a platinum crucible (containing 0.5 g of Na2CO3) with three 0.5-g rinses of Na2CO3. Add sufficient Na2CO3 to bring the total Na2CO3 content to 6 g. Cover the crucible, and fuse gently over a bunsen burner. 13.1.1 When fusion is complete (usually 30 min to 1 h), remove the crucible from the burner, swirl to distribute the melt on the sides of the crucible, and allow to cool. Then place the crucible and contents in a 200-mL high-form beaker and add 25 mL of water. Cover the beaker with a watch glass, and cautiously add HCl (1+1) to decompose the melt. When solution of the melt is complete, boil for several minutes on a hot plate and cool. 13.1.2 Transfer to a 100-mL volumetric ask, dilute to volume, and mix. Transfer a suitable aliquot of this solution to a 100-mL volumetric ask.
2

C560 88 (2010)1
13.2 Color DevelopmentAdjust the pH of the aliquot to 6 to 8 with Na2CO3 solution, then proceed in accordance with 13.2. 13.3 PhotometryProceed in accordance with 12.3. 13.4 CalibrationConvert the photometric reading of the sample solution to micrograms of silicon by means of the calibration curve. 14. Calculation 14.1 Calculate the parts per million (ppm) of silicon in the original sample as follows:
Silicon, ppm ~A 3 B!/W

where: A = silicon per 100 mL of solution found in the aliquot used, g, B = aliquot factor = original volume divided by aliquot taken for analysis, and W = original sample weight, g. IRON BY THE ORTHO-PHENANTHROLINE (PHOTOMETRIC) TEST METHOD 15. Summary of Test Method 15.1 After suitable dilution of an aliquot from the carbonate fusion is adjusted to a pH of 3.0, the iron is reduced with hydroxylamine hydrochloride. The ferrous orthophenanthroline complex is formed, and its absorption is measured at a wavelength of 490 nm. 16. Stability of Color 16.1 The color becomes stable within 15 min and does not change for at least 48 h. 17. Interferences 17.1 No interfering elements are normally present in graphite. 18. Reagents 18.1 Ammonium Hydroxide (NH4OH) (1+1)Mix equal volumes of concentrated NH4OH, sp gr 0.90 and water. 18.2 Bromine WaterAdd 10 mL of bromine to 1 L of water. Allow to stand for 24 h. 18.3 Hydrochloric Acid (HCl) (1+1)Mix equal volumes of concentrated HCl, sp gr 1.19 and water. 18.4 Hydroxylamine Hydrochloride SolutionDissolve 10 g of hydroxylamine hydrochloride (NH2OHHCl) in water and dilute to 100 mL. Discard the solution if color develops on standing for long periods of time. 18.5 Iron, Standard Solution (1 mL = 0.1 mg Fe)Into a 100-mL beaker, weigh 0.1000 g of iron wire. Dissolve the wire in 50 mL of HCl (1+1). Add 1 mL of bromine water to oxidize the iron to the ferric state. Boil the solution to expel the excess bromine and dilute to 1 L in a volumetric ask. 18.6 Iron Wire, primary standard, over 99.9 % pure. 18.7 o-Phenanthroline Dissolve 2 g of 1,10phenanthroline in ethyl alcohol and dilute to 250 mL with ethyl alcohol in a volumetric ask. Discard this solution if color develops upon long standing.
Copyright by ASTM Int'l (all rights reserved);

19. Preparation of Calibration Curve 19.1 Calibration SolutionsTransfer 0.0, 1.0, 2.0, 3.0, 4.0, 5.0, and 6.0 mL of iron solution (1 mL = 0.1 mg Fe) to 100-mL volumetric asks. Add NH4OH (1+1) until the brown hydrous precipitate of ferric hydroxide (Fe(OH)3) is just visible. Then add HCl (1+1) drop-wise, while stirring, until the precipitate just dissolves. Bring the pH of the solution to 3.0 by adding 2 additional drops of HCl (1+1). Then add 2 mL of NH2OHHCl solution. 19.2 Color DevelopmentHeat the solutions in the asks almost to boiling. Add 1 mL of o-phenanthroline solution and allow the solutions to cool. Then dilute to the mark with water. 19.3 PhotometryTransfer a suitable portion of the reagent blank solution to a 1-cm absorption cell, and adjust the spectrophotometer to the initial setting using a wavelength of 490 nm. While maintaining this photometer adjustment, take the photometric readings of the calibration solutions. 19.4 Calibration CurvePlot the absorbance of the calibration solution against micrograms of iron per 100 mL of solution. 20. Procedure 20.1 Sample SolutionProceed in accordance with 13.1. 20.2 Color DevelopmentProceed in accordance with 19.2. 20.3 PhotometryProceed in accordance with 19.2. 20.4 CalibrationConvert the photometric reading of the sample solution to micrograms of iron by means of the calibration curve. 21. Calculation 21.1 Calculate the ppm of iron in the original sample as follows:
Fe, ppm ~A 3 B!/W

where: A = iron per 100 mL of solution in the aliquot used, g, B = aliquot factor = original volume divided by aliquot taken for analysis, and W = original sample weight, g. CALCIUM BY THE PERMANGANATE (COLORIMETRIC) TEST METHOD 22. Summary of Test Method 22.1 Calcium is precipitated as the oxalate, ltered off, and dissolved in sulfuric acid. The acid solution is added to a dilute potassium permanganate solution, and the decrease in absorption is measured at a wavelength of 528 nm. 23. Stability of Color 23.1 Potassium permanganate solution is decomposed rapidly by exposure to air or light. Photometric readings should be made at once. 24. Interferences 24.1 Ashed graphite samples are normally free of signicant concentrations of possible interfering ions.
3

C560 88 (2010)1
25. Reagents 25.1 Ammonium Hydroxide (NH4OH2) (1+6)Mix 1 volume of concentrated NH4OH2, sp gr 0.90 with 6 volumes of water. 25.2 Ammonium Oxalate SolutionPrepare a saturated solution of ammonium oxalate ((NH4)2C2O42H2O). 25.3 Bromocresol Green Indicator SolutionUse the water soluble sodium salt. Dissolve 0.040 g in water and dilute to 100 mL. Store in a glass-stoppered brown bottle. 25.4 Formate Buffer Solution (pH 3.7)Dissolve 31.5 g of ammonium formate in about 200 mL of water and transfer to a 1-L volumetric ask. Add 20.8 mL of formic acid, dilute to volume, and mix well. 25.5 Hydrochloric Acid (HCl) (1+1)Mix equal volumes of concentrated HCl, sp gr 1.19 and water. 25.6 Oxalate, Standard Solution (1 mL = 0.125 mg Ca) Dry approximately 2 g of sodium oxalate (Na2C2O4) at 105C for 1 h, and cool in a desiccator. Weigh accurately 0.2090 g into a 250-mL beaker, dissolve in boiled water, and dilute to 500 mL in a volumetric ask. 25.7 Potassium Permanganate, Standard Solution Dissolve 3.25 g of NIST potassium permanganate (KMnO4) in 1 L of hot water. Let stand in the dark for 12 h. Filter through inert lter medium into a dark colored bottle. 25.7.1 Standardize as follows: dissolve 3.0 g of dried NIST sodium oxalate (Na2C2O4) in boiled water and dilute to 500 mL in a volumetric ask. Pipet 25-mL aliquots of the oxalate solution into 600-mL beakers. Add 250 mL of H2SO4 (1+33), heat to 55 to 60C, and titrate to a faint pink end point that persists for 30 s. For a blank, add permanganate solution, dropwise, to 250 mL of H2SO4 (1+33). Note the volume required to impart a pink color. Calculate the normality of the permanganate solution. 25.7.2 Prepare 0.0200 N KMnO4 solution by appropriate dilution of the standardized solution. 25.8 Sulfuric Acid (H2SO4) (1+3)Carefully mix 1 volume of concentrated H2SO4, sp gr 1.84 with 3 volumes of water. 26. Preparation of Calibration Curve 26.1 Calibration SolutionsTransfer 0.0, 5.0, 10.0, 15.0, and 25.0 mL of standard oxalate solution into 100-mL volumetric asks. Add 40 mL of H2SO4 (1+3) and 10 mL of boiled and cooled water. Place the asks in a water bath at 55 to 60C for 5 min. 26.2 Color DevelopmentPipet into each ask 10.0 mL of the 0.0200 N KMnO4 solution. Remove from the bath and allow to stand at room temperature for 5 min for the color change to be completed. Place in a cold-water bath, and cool to room temperature. Dilute to volume with CO2-free water and mix. 26.3 PhotometryTransfer a portion of the reagent blank solution to a 1-cm absorption cell. Transfer a portion of the rst standard into a second absorption cell. Adjust the spectrophotometer to zero, with the standard in the light path. Then measure the absorbance of the reference solution. Repeat the procedure using the other standard solutions.
Copyright by ASTM Int'l (all rights reserved);

26.4 Calibration CurvePlot the absorption of the calibration solutions against micrograms of calcium per 100 mL of solution. 27. Procedure 27.1 Sample SolutionProceed in accordance with 13.1. However, after the sample solution has been diluted to volume and mixed, proceed as follows: pipet a suitable aliquot (usually 25 mL) into a 50-mL beaker. Add 1 or 2 drops of bromocresol green indicator, 1 mL of formate buffer, and 1 mL of saturated (NH4)2C2O4 solution. Add, dropwise, NH4OH (1+6) to the appearance of a faint blue color (pH = about 4.6). Then add HCl (1+1) dropwise with stirring, to obtain a very light yellow color (pH = 3.8). Digest in a water bath at a temperature of 90C for 10 to 15 min. Remove from the water bath and allow to digest at room temperature for at least 30 min. Filter through a 15-mL, medium-porosity fritted-glass crucible, and wash with four 2-mL portions of cold water. Remove the crucible from the holder and rinse off the outside and bottom thoroughly. Discard all ltrates and washings. Place the crucible back on the ltration assembly. Pour four 10-mL portions of hot H2SO4 (1+3) (slowly with stirring) into the beaker and then into the crucible. Collect the solution and four 2.5-mL hot water washings in a 100-mL volumetric ask, and place in a hot water bath at 55 to 60C for 5 min. 27.2 Color DevelopmentProceed in accordance with 26.2. 27.3 PhotometryProceed in accordance with 26.3. 27.4 CalibrationConvert the photometric reading of the sample solution to micrograms of calcium by means of the calibration curve. 28. Calculation 28.1 Calculate the ppm of calcium in the original sample as follows:
Ca, ppm 5 ~A 3 B!/W

where: A = calcium per 100 mL of solution in the aliquot used, g, B = aliquot factor = original volume divided by the aliquot taken for analysis, and W = original sample weight, g. ALUMINUM BY THE 2-QUINIZARAN SULFONIC ACID(PHOTOMETRIC) TEST METHOD 29. Summary of Test Method 29.1 The bulk of the water is removed by evaporation, and the moist residue is taken up in absolute methanol. The color reagent is added, and the pH is adjusted with concentrated hydrochloric acid, if necessary. The absorption of the colored solution is measured at a wavelength of 560 nm. 30. Stability of Color 30.1 The solution is stable for at least 24 h. 31. Interferences 31.1 Iron and titanium are the only ions that might interfere. However, they do not interfere in the amounts usually present
4

C560 88 (2010)1
in graphite. If a sample contains more than 500 ppm of iron, or more than 40 ppm of titanium, they are removed by electrolysis in a mercury cell. 32. Reagents 32.1 Aluminum, Standard Solution (1 mL = 1 mg Al) Weigh out 6.95 g of aluminum nitrate (Al(NO3)39H2O), and transfer to a 500-mL volumetric ask. Cover the salt with 200 mL of absolute methanol. Add 10 mL of concentrated hydrochloric acid (HCl, sp gr 1.19) to dissolve the salt, and dilute to volume with absolute methanol. For use dilute 10 mL of this solution to 1 L with absolute methanol (1 mL = 0.01 mg Al) for a working aluminum solution. 32.2 Hydrochloric Acid (HCl) (sp gr 1.19)Concentrated HCl. 32.3 Hydrochloric Acid (1+1)Mix equal volumes of concentrated HCl (sp gr 1.19) and water. 32.4 Methanol, Absolute. 32.5 2-Quinizarin Sulfonic Acid SolutionDissolve 0.16 g of 2-quinizarin sulfonic acid in absolute methanol, dilute to 500 mL with absolute methanol, and store in a polyethylene bottle. 33. Preparation of Calibration Curve 33.1 Transfer 0.0, 1.0, 3.0, 5.0, 7.0, and 10.0 mL of the working aluminum solution to 100-mL volumetric asks. 33.2 Color DevelopmentAdd 10 mL of 2-quinizarin sulfonic acid solution, dilute to volume with absolute methanol, and mix. The acidity should be within the desired limits of pH 0.3 to 0.5, as measured with a pH meter. (If the solution is on the basic side, adjust to the desired range with concentrated HCl (sp gr 1.19). Let stand 1 h. 33.3 PhotometryTransfer a portion of the reference solution to a 1-cm absorption cell and adjust the photometer to the initial setting, using a wavelength of 560 nm. While maintaining this photometer adjustment, take the photometric readings of the calibration solutions. 33.4 Calibration CurvePlot the absorbance of the calibration solutions against the micrograms of aluminum per 100 mL of solution. 34. Procedure 34.1 Ash DissolutionProceed in accordance with 13.1. Transfer the aliquot from the sample solution to a platinum dish, add 1 drop of HCl (1+1), and evaporate the solution to a volume of 0.5 to 1.0 mL on a sand bath. Remove, cool, and add 5 mL of absolute methanol to the dish. Rub with a policeman to ensure complete solution of the aluminum salt. Transfer the solution to a 100-mL volumetric ask, and rinse the dish with three 5-mL portions of absolute methanol, adding these to the solution in the volumetric ask. 34.2 Color DevelopmentProceed in accordance with 33.2. 34.3 PhotometryProceed in accordance with 33.2. 34.4 CalibrationConvert the photometric reading of the sample to micrograms of aluminum by means of the calibration curve.
Copyright by ASTM Int'l (all rights reserved);

35. Calculation 35.1 Calculate the ppm of aluminum in original sample as follows:
Aluminum, ppm 5 ~A 3 B!/W

where: A = aluminum per 100 mL of solution in the aliquot used, g, B = liquot factor = original volume a divided by the aliquot taken for analysis, and W = original sample weight, g. TITANIUM BY THE PEROXIDE (COLORIMETRIC) TEST METHOD 36. Summary of Test Method 36.1 Hydrogen peroxide is added to form the peroxytitanium complex. The absorption of the yellow solution is measured at a wavelength of 409 nm. 37. Stability of Color 37.1 The yellow colored complex is stable for over 2 years. 38. Interferences 38.1 No interfering ions are normally present in ashed graphite samples. 39. Reagents 39.1 Hydrochloric Acid (HCl) (1+1)Mix equal volumes of concentrated HCl, sp gr 1.19 and water. 39.2 Hydrogen Peroxide (H2O2) (30 %)Concentrated H2O2. 39.3 Potassium Pyrosulfate (K2S2O7). 39.4 Sodium Carbonate Solution (Na2CO3) (100 g/L) Dissolve 100 g of Na2CO3 in water and dilute to 1 L. 39.5 Sodium Hydroxide Solution (NaOH) (100 g/L) Dissolve 100 g of NaOH in water and dilute to 1 L. 39.6 Sulfuric Acid (H2SO4) (1+7)Carefully mix 1 volume of concentrated H2SO4, sp gr 1.84 with 7 volumes of water. 39.7 Sulfuric Acid (1+33)Carefully mix 1 volume of concentrated H2SO4 (sp gr 1.84) with 33 volumes of water. 39.8 Titanium, Standard Solution (1 mL = 0.6 mg Ti)Fuse 0.5 g of titanium dioxide (TiO2) with 10 to 12 g of potassium hydrogen sulfate (KHSO4) in a platinum dish, keeping at fusion heat until the oxide has dissolved. Avoid heating to high temperature. Allow the melt to cool, dissolve in 20 to 25 mL of H2SO4 (1+7), and dilute to volume with H2SO4 (1+7) in a 500-mL volumetric ask. 40. Preparation of Sample 40.1 Add sufficient sample of graphite to give at least 50 mg of ash (see Test Method C561). Fuse the ash with Na2CO3 as described in 13.1. After the fusion has cooled, place the crucible and lid in a 250-mL high-form glass beaker, add 100 mL of water, and digest on a sand bath until solution is complete. Dissolve any residual melt in the crucible by adding several drops of HCl (1+1) and rinse into the main solution. Then add 1 mL of NaOH solution (100 g/L) and boil the solution for 15 min. Remove from the hot plate and cool the
5

C560 88 (2010)1
solution to room temperature. (The solution must be cooled before ltering to prevent loss of TiO2 through solution in hot carbonate solution.) Filter the solution through rapid-ltering paper, wash the precipitate twice with Na2CO3 solution (100 g/L), and three times with cold water. Collect the ltrate and washings and reserve for the determination of vanadium. 40.2 Dissolve the precipitate on the paper with HCl (1+1), collecting the solution in a 100-mL volumetric ask. (Keep the nal volume below 75 mL.) If any residue remains on the paper, transfer the lter paper to a platinum crucible, burn off the paper, and ignite to completely ash the paper. Allow the crucible to cool, then add 5 g of K2S2O7 to the residue. Slowly heat the crucible to the lowest temperature that will melt the pyrosulfate. Maintain at this temperature until the fusion is complete. Remove the crucible from the ame and allow to cool. Then dissolve the melt in 10 mL of H2SO4 (1+33). When solution is complete, add it to the acid solution in the 100-mL volumetric ask. Rinse the crucible with three 2-mL portions of H2SO 4 (1+33) and add to the main solutions. Dilute to volume with H2SO4 (1+33). 41. Preparation of Calibration Curve 41.1 Calibration SolutionsTransfer 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0 mL of titanium standard solution (1 mL = 0.6 mg Ti) to 100-mL volumetric asks. Dilute nearly to volume with H2SO4 (1+33). 41.2 Color DevelopmentAdd 2 mL of concentrated H2O2 (30 %) to each ask, and dilute to 100 mL with H2SO4 (1+33). 41.3 PhotometryTransfer a portion of the reagent blank solution to a 1-cm absorption cell, and adjust the photometer to the initial setting, using a wavelength of 409 nm. While maintaining this setting, take the photometric readings of the calibration solutions. 41.4 Calibration CurvePlot the absorbance of the calibration solutions against micrograms of titanium per 100 mL of solution. 42. Procedure 42.1 Transfer a suitable aliquot, usually 50 mL of the sample solution, to a 100-mL volumetric ask. Dilute nearly to volume with H2SO4 (1+33). 42.2 Color DevelopmentProceed in accordance with 41.2. 42.3 PhotometryProceed in accordance with 41.3. 42.4 CalibrationConvert the photometric reading of the sample solution to micrograms of titanium by means of the calibration curve. 43. Calculation 43.1 Calculate the ppm of titanium in the original sample as follows:
Titanium, ppm 5 ~A 3 B!/W

W = original sample weight, g. VANADIUM BY THE 3,3*-DIMETHYLNAPHTHIDINE (COLORIMETRIC) TEST METHOD 44. Summary of Test Method 44.1 Vanadium in solution reacts with 3,3 8dimethylnaphthidine to form a stable, colored solution. This method is much more sensitive and much freer from interferences than is the classical phosphotungstate method. 45. Stability of Color 45.1 The colored complex is stable for at least 24 h. 46. Interferences 46.1 Heavy metal oxides interfere. However, these elements are absent when the ltrate obtained in accordance with 40.1 is used for the vanadium determination. 47. Reagents 47.1 3,38-Dimethylnaphthidine Solution Dissolve 0.5 g of 3,38-dimethylnaphthidine in approximately 400 mL of glacial acetic acid. Warm gently until the reagent dissolves, cool and dilute to volume with glacial acetic acid in a 500-mL volumetric ask. 47.2 Hydrochloric Acid (HCl) (1+1)Mix equal volumes of concentrated HCl (sp gr 1.19) and water. 47.3 Perchloric Acid (60 %)(HClO4). 47.4 Phosphoric Acid (H3PO4) (1+1)Mix equal volumes of concentrated H3PO4, 85 % and water. 47.5 Vanadium, Standard Solution (1 mL = 10 g V) Weigh 0.2296 g of NIST ammonium vanadate (NH4VO3) into a 250-mL beaker. Add 10 mL of HClO4 (60 %) and heat to strong fumes. Cool, transfer to a 1-L volumetric ask, dilute to volume, and mix. Dilute 50 mL of this solution to 500 mL in a volumetric ask. This working solution contains 10 ppm of vanadium. 48. Preparation of Sample 48.1 See 40.1 and 40.2. 49. Preparation of Calibration Curve 49.1 Calibration SolutionsTransfer 0.0, 1.0, 4.0, 7.0, 10.0, and 13.0 mL of the vanadium solution to 50-mL volumetric asks. Bring this volume in the asks to 25 mL with water and add 6 mL of HClO4 (60 %) and 10 mL of H3PO4(1+1). 49.2 Color DevelopmentAdd 5 mL of 3,38dimethylnaphthidine solution to each ask, dilute to volume, and mix. Let stand for 15 min. 49.3 PhotometryTransfer a portion of the reference solution to a 1-cm absorption cell and adjust the photometer to the initial setting using a wavelength of 550 nm. While maintaining this photometer adjustment, measure the absorbance of the calibration solutions. 49.4 Calibration CurvePlot the absorbance of the calibration solutions against the micrograms of vanadium per 50 mL of solution.
6

where: A = titanium per 100 mL of solution in the aliquot used, g, B = aliquot factor = original volume divided by the aliquot taken for analysis, and
Copyright by ASTM Int'l (all rights reserved);

C560 88 (2010)1
50. Procedure 50.1 Acidify the ltrate obtained in accordance with 40.1 with HCl (1+1), and evaporate to a volume of 70 to 80 mL. Cool, and transfer to a 100-mL volumetric ask. Adjust the solution to pH 6 with HCl using test paper, dilute to volume with water, and mix. Transfer an aliquot equivalent to 1 or 2 g of the original sample into a 50-mL volumetric ask. Bring the volume to 25 mL and add 6 mL of HClO4 (60 %) and 10 mL of H3PO4 (1+1). 50.2 Color DevelopmentProceed in accordance with 49.2. 50.3 PhotometryProceed in accordance with 49.3. 50.4 CalibrationConvert the photometric reading of the sample solution to micrograms of vanadium by means of the calibration curve. 51. Calculation 51.1 Calculate the ppm of vanadium in the original sample as follows:
Vanadium, ppm 5 ~A 3 B!/W

55.3 Curcumin-Oxalic Acid ReagentPrepare standard alcohol by adding 35 mL of water to 1 L of anhydrous ethanol. Dissolve 7.50 g of oxalic acid (H2C2O42H2O) in about 350 mL of the standard alcohol, then add 12.5 mL of concentrated hydrochloric acid (HCl, sp gr 1.19), 37.5 mL of water, and 0.1750 g of nely ground curcumin. Dilute to 500 mL with standard alcohol. (Filter if cloudy.) Store in a plastic bottle in a dark place. Make a fresh solution every ten days. 55.4 Extraction AlcoholAdd 200 mL of water to 800 mL of anhydrous ethanol. Mix thoroughly and store in a plastic bottle. 55.5 Hydrochloric Acid (1+11)Mix 1 volume of concentrated hydrochloric acid (HCl, sp gr 1.19) with 11 volumes of water. 56. Preparation of Calibration Curve 56.1 Transfer 0.0, 0.5, 1.0, 2.0, 3.0, and 4.0 mL of the working boron solution (1 mL = 1 g B) to 100-mL platinum dishes. Stir the calcium hydroxide (Ca(OH)2) suspension, and rapidly transfer 10.0 mL of the suspension to each dish. Swirl the mix, and evaporate to dryness on a sand bath. (Caution Avoid spattering during the evaporation.) Transfer the dishes to a muffle furnace and heat at 650C until all of the carbon has burned off. (The ashing can be accelerated by admitting air into the furnace through a tube connected to the compressed air line. However, the ow must be carefully adjusted to prevent the material in the dishes from being blown out of the dishes.) After all the carbon has been burned off (requires about 18 h), remove the dishes from the furnace and cool in a desiccator. 56.2 Color DevelopmentAdd 6 drops of HCl (1+11) to the residues in the dishes, swirling to dissolve all of the material. Then add 1 mL of a saturated alcoholic solution of H2C2O42H2O, and 5.0 mL of curcumin-oxalic acid reagent. Float the dishes on the surface of a water bath maintained at 55 to 60C. When dry, allow the dishes to remain 3 min longer, then remove and cool. The water bath shall be enclosed so that a constant humidity can be maintained. Extract the colored complex with about 10 mL of the extraction alcohol, rubbing with a policeman to assist complete solution. Transfer the extract to a 50-mL volumetric ask, and rinse the dish thoroughly with small portions of the extraction alcohol. Make sure that all of the colored material has been rinsed from the platinum dish. Then dilute to volume with extraction alcohol and mix. 56.3 Reference SolutionStir the Ca(OH)2 suspension and transfer 10.0 mL to a platinum dish. Then proceed in accordance with 56.1. 56.4 PhotometryFilter a portion of the reference solution through a rapid-ltering paper directly into a 1-cm absorption cell, and adjust the photometer to the initial setting, using a wavelength of 555 nm. While maintaining this photometric adjustment, measure the absorbance of the calibration solutions. 56.5 Calibration CurvePlot the absorbance of the calibration solutions against the micrograms of boron per 50 mL of solution. 56.5.1 The analytical recovery of boron involves serious problems of reproducibility with respect to the effect of changes in humidity, evaporation rate, and so forth on the
7

where: A = vanadium per 50 mL of solution in the aliquot used, g, B = aliquot factor = original volume divided by the aliquot taken for analysis, and W = original sample weight, g. BORON BY THE CURCUMIN-OXALIC ACID (COLORIMETRIC) TEST METHOD 52. Summary of Test Method 52.1 After ashing the sample, the residue is acidied and the color is developed by adding curcumin-oxalic acid solution and evaporating to dryness on a water bath. The colored complex is extracted with alcohol, and the absorption of the complex is measured at 555 nm. 53. Stability of Color 53.1 The colored complex is stable for several hours if kept dry. After extracting with alcohol, photometer readings must be made within 2 h. 54. Interferences 54.1 No interfering ions are usually present in the ashed graphite samples. 55. Reagents 55.1 Boron, Standard Solution (1 mL = 200 g B) Dissolve 1.1435 g of boric acid in water, dilute to 1 L in a volumetric ask, and mix thoroughly. For use, dilute 5.0 mL of this solution to volume in a 1-L volumetric ask for a working boron solution (1 mL = 1 g B). 55.2 Calcium Hydroxide SuspensionIgnite approximately 10 g of calcium carbonate (CaCO3) in a platinum dish at a temperature of 950C for 1 h. Cool in a desiccator, and grind in a mullite mortar to pass a No. 200 (75-m) sieve. Add 2.8 g of the calcium oxide (CaO) to 1 L of water. Store in a tightly stoppered plastic bottle.
Copyright by ASTM Int'l (all rights reserved);

C560 88 (2010)1
solutions. It is necessary, therefore, that a new calibration curve be drawn for each set of samples. An alternative is to include a standard sample of graphite of known boron content with each set of samples. The calibration curve is drawn from the absorbance obtained. 57. Procedure 57.1 Weigh a sample of graphite approximately 3 g to an accuracy of 0.1 mg into a tared platinum dish. Proceed in accordance with 56.1. 57.2 Color DevelopmentProceed in accordance with 56.2. 57.3 Reference SolutionProceed in accordance with 56.3. 57.4 PhotometryProceed in accordance with 56.4. 57.5 CalibrationConvert the photometric reading of the sample solution to micrograms of boron by means of the calibration curve. 58. Calculation 58.1 Calculate the ppm of boron in the original sample as follows:
Boron, ppm 5 ~A 3 B!/W

where: A = boron per 50 mL of solution in the aliquot used, g, B = aliquot = original volume divided by the aliquot taken for analysis, and W = original sample weight, g. 59. Report 59.1 The report shall include the following: 59.1.1 Proper identication of the sample, and 59.1.2 Results obtained from at least two analytical determinations, and their average. 60. Keywords 60.1 calibration; calibration solutions; chemical analysis; color development; graphite; photometry

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every ve years and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, at the address shown below. This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website (www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/ COPYRIGHT/).

Copyright by ASTM Int'l (all rights reserved);